Amides of 2-aminoarylenethiazoles



Patented Apr. 23, 1946 AMIDES or Z AMINOARYLENETHIAZOLES Ernst Henzi, Basel, SWitze rIand aSsignOr to Society of Chemical Industry ln=Basle, Basel, 7

Switzerland No Drawing. Application January 26,1942, se-

rial No. 428,319. In Switzerland February 6,

6 Claims. (01. 266-305) It has been found that new amides are obtained if 2-aminoarylenethiazols are allowed to react upon aromatic hydroxycarboxylic acids which couple with diazo compounds the 'ortho position to theOH-group. This reactioncan take .p1ace'acor in to known methods, such as by conden'sing the halides of the acids concerned with the 2-aminoarylenethiazols. Amides of the newt'ype. are also Obtained vwhen the acids concerned are heated with the arylenethiazols in l estion'and dehydrating agents, such as phos 'phorous trichloride or phosphorus oxychloride,

in. the presence of suitable diluents, which, if desired, can also act as acid-binding agents. Tolutine, .chlorobenzene, dimethylaniline, pyridine, fetd jareexamples of such diluents/ I .1 -Ar'iiong .the' hydroxycarboxylicacids which "co e into question for the manufacture of the droxynaphthalene-6-pheny1amino 3 carboxylic acid, 2-hydroxynaphthalene 6 bromo 3 car- .boxylic Lacid, 2-,hydroxyanthracene-3;-carboxylic ,acid, etc. "In the termaromatic hydroxycarboxylic acidsf are included also heterocyclic hydroxycarboxylic acids in which the OH-groupis I I I aromaticany combined, Such as 01x34! I in which R stands for an aromatic radical m .diphenyleneoxidev3- or -2- carboxy1ic acid, 2-,hy-

droxycarbazole-3-carboxylic acid, hydroxycarbazole-3-carboxylic, acid, -hydroxy a-naphthocarbazole-fi-carboxy1ic acid 7-hydroxyfa-naphthocarbazole-6-carbokylic acid 0H s 3' methyl 7 hydroxya -naphthocarbazole-6- carboxylic acid a in 10 Among the 2- aminoarylenethiazols, which can also be used in the preparation of the new amides, mention may be made of 2-aminobenzthiazol, 2- -amino-6- -methoxyor -6-ethoXy1oenzthiazol, 2- amino -fi-chloro benzthiazol, 2-amino-4-methyl- -ben'zthiazolg 2-aminof-4 methyl-fi-chlorobenzthiazdl, 2-amino-6-methylbenzthiaaol, 2'-amino-6 '7- bnzobenzthiazol, 2 amino 2 methoxy 6:7- behzoberizthiazdl; as well as diamiIio-dithiazols, which can then'be combined'with 2 molecules of the hydroxycarboxylic acid. Such diamino-dithiazols are obtained, for xample, by condensationof 2 molecules of thiocyanic acid with 1 moleculeof the corresponding diamine, such as benzi- -dine or 4:4 -diaminodipheny1ene oxide,

25 J The new amides thus correspond to the general which the OH-group is united in such a manner that dia'zo compounds react with this aromatic [radical withformationof ortho-hydroxyazo dyestuffs; Furthermore, in the above general for- Lr'nula, gcdenotes a whole number not less than one and not greater than two, and R1 denotes an aromatic', radical to which the sulphur atom and the nitrogen atom oftheatom grouping;

are *united'in the ortho position to one another. Both radicals, R and R1 can belong to the most varied-aromatic series, for example, to the benzene series, the naphthalene series, the anthracene series, the diphenyl series, the diphenylmethane series, etc. :iFurthermore, in this respect, refer- 5 ence is made to the second paragraph of the specification. These varied possibilities are illustrated below'by a, series of special cases. Those (amides are especially valuable in which the 0H- ..grqup sta'n in theortho position to the f e-am? group and, among these, those in which the group corresponds, tothe atomic 'grouping of 2- hydroxynaphthoic acid and its pure substitution products which are capable of coupling. Thanks to the presence of the OH-group, the

new amides possess the property of iorming wa-,

ter-soluble alkali salts, as well as that of unitin with diazo compounds to yieldazodyestufisv 'In T the form of their solutionsin-'caustic-alkalis'they'-" possess a pronounced affinity for vegetable fibres,

so that they can be used with successior theprep-, aration of dyeings on the most varieditextile ma:

terials, such as cotton, regenerated cellulose, na-

tural silk, wool, ramie, etc., by th methods. in

Here also, those radicals are to be understood as aromatic radicals which consist of aromatic nuclei united together by bridges of a non-aromatic nature. Thus, for example, not only benzene and toluene radicals are to be considered as aromatic radicals of the benzene series, but also radicals of diphenylether, azobenzene, diphenylamine,

benzanilide, etc.

In this case also, the above general formula Such bases are, for example, the chlorbenzene, l-amino 2 nitro-fi-methylb nz n amino-2-methyle4 or 5-nitrobenzene, as well as phenol others, ,such as 1-amino-2-methoxy-4- chlorobenzene, 1-amino-2-methoxy-4- or -5-nitrobenzene, 2-amino-4- chlorodiphenylether, 2-

dichlorodiphenylether, .2 amino-2 :4 :4-trichlorodiphenylether, 2-amino-2'- or -3'- or, -'-meth- .lY'4-chlorodiphenylether, 2 amino i-chlorobenzene-l-benzyl ether, ;4.-amino-4-methoxydiphenylamine, 4-amino-2:5 -dimethoxyor 2:5-dieth-;

oxy 1,-, benzoylaminobenzene, 1 amino-2:5-dimethoxy- .or 2:5-.diethoxy-l-(2'- or 4'-methyl)- phenoxyacetylaminobenzene, 4 amino 2.:5 diethoxyor 2:5-dimethoxyel-carbethoxyamino.

amino-4:4'-dichlorodiphenylether, 2-amino-2' :4-;

benzene, benzidine, dianisidine, a-naphthylamine,

etc., furthermore, amino-azo dyestuffs, such as e-aminoazobenzene, 4-amino-2-methoxyazobenzene, 4-amino-3:2'-dimethylazobenzene, 4-amino 4' methylazobenzene, 4-an ino-4'-nitroazobenzene, 4 amino-2'-chloro-4' nitroazobenzene, i-amino 2:5- d'imethoxy-i'-nitroazobenzene, 4-

' amino-2 5-diethoxy-4' nitroazobenzene, 4-ami} no- 2 5-dimethoxy-2'-chloro- 4 nitroazoben zene, 4 amino-3-methoxy -4'-nitroazobenzene, 4-amil:e -diaminoazoben'zene, 4:4'-diamin'o 3 methoxy-fi-znethylazobenzene, 4-aminonaphthalene 1- azoberlzene, i': ifQdiaminonaphthalene-l-azobenzene, 4-amino-naphthalene-2'-methoxy 1 azo- I described and-R2 stands for the radical orally 1 no 3 methoxy 6 -'methy1-4-nitroazobenzene,

h 7 0 'in'which-R, in and 3B} have the meanings already desired aromatic radical-for example, a. radical of the benzene, naphthalene or diphenyl series.

azol, I methylbenzthiazol, 2-amino-5 methylbenzthiazol,

will be illustrated by a number of examples which will be found below.

As already mentioned, these new dyestuffs can be prepared. on the fibre itself. If they are used in printing, the diazotizing components can be used in the form oi N-nitrosamines or in the form of water-soluble salts of diazoamino compounds.

7 Example 1 I 188 parts of 2 hydroxynaphthalene- 3ecarboxylic acid and .19 4 parts of 2-,amino-6-ethoxybenzthiazol are heatedwith 1000 parts of chlorobenzene to 75 C. 46'parts of phosphoroustrichloride are dropped into this mixture in the, course of 1 hour, after which the reaction mixture is heated at the boil until no more hydrochloric acid is evolved. After cooling, the precipitated condensation product is filtered off. Tracesof solvent are removed with steam in the presence of an excess of sodium acetate; the condensation product is then filtered, washed. with water anddried.

The chlorobenzene can be replaced by'other solvents, such as toluene or dimethylaniline. Phosphorous hydroxychloride, .for example, or thionyl chloride or silicon tetrachloride .can'be used in place of phosphorous trichloride.

The new amide corresponds to the formula S It can be converted into an alkali salt preferably by triturating with alcohol, Turkey red oil andsodium hydroxide solution of 40 percent strength,

the aqueous solutions'of which possess an entirely surprising affinity for cellulose, for example vegetable fibers. T f

The amides from 2-amino-6-lmethoxybenzthi- 2-amino-S-chlorobenzthiazol, 2-amino-6- Z-amino-brizthiazol etc. behave similarly. 7

Example 2 206.5 parts of 2-hydroxynaphthalene-3-carboxylic acid chloride and parts of 2-amino-6- methoxybenzthiazol are heated slowly to the boil with 1200 parts of chlorobenzene and are boiled for 12 hours under reflux with stirring. After cooling, the precipitated condensation product ,is filtered 01f and traces of solvent are removed with steam in the presence of so much sodium carbonate that a weakly alkaline solution is formed. The pale yellow condensation product is then filtered off, washed with hot water and dried. It melts at 300-302 C. The new amide corresponds to the formula 1 i Example 3 18a parts of 2I-hydroiqznaphthalene-3 carboxylic acid. and 180 parts. of z-amino-d-methoxybenzthiazol are heated to IO-80 C. in 1000 parts of diethylaniline, 46 parts of phosphorous trichloride are dropped into this mixture during the courseof 'an hour, and the reaction mixture is then heated to 130 14050- for 4 hours. After cooling, the reaction mass is introduced into an excess of hydrochloric acid whilst stirring. .The precipitated condensation product is filtered off andwashed with hot'water. To purify it it is dissolved in dilute caustic soda by addition of alcohol and is reprecipitated by carbonic acid. The condensation product. has the same formula as the .product of Example 2.

Example 4 152 parts of 1-methyl-4-hydroxybenzene-5- carboxylic acid and 194 parts of 2-amino-6- ethoxybenzthiazol are heatedto 70-80 0. in 1200 parts of chlorobenzene. 69 parts of phosphorous trichloride are dropped into this mixture in the course of 1 hour, when the reaction mixture is boiled until no more hydrochloric acid is evolved. After cooling, 100 parts'of sodium acetate crystals are added, and the chlorobenzene is removed by steam distillation. The new condensation product which is precipitated is filtered off, washed with hot water and dried. To purify it, it is recrystallized from boiling glacial acetic acid. It melts at 264-265 C.

The new pale yellow condensation product has the formula Instead" of 1-methyl-4-hydroxybenzene-5-carboxylic acid, salicylic acid, xylenolcarboxylic acidor 4-benzoylphenol-ortho-carboxylic acid, etc... can be used.

Example 5 until no more hydrochloric acid is evolved.

After cooling, the new condensation product-is filtered off and, after addition of sumclent so dium carbonate to give a weakly alkaline solu' tion, is freed from solvent by steam distillation. The precipitated condensation product, which possesses the formula -O CaHA is filtered, washed with hot water and drleduj H :Instead oi chlorobenaene tolueneor mane can .15

be used a diluent; dimethylaniline or diethylaniline can also be used as a basic solvent, when the condensation product can be worked up as described in Example 3'.

Example 6 dried. 'For further purification, for example, it can be recrystallized from boiling pyridine.

The product melts at 304 C.

The new condensation product has the formula on N r N no (IE- (1.11 -.00 o s s 0 The carboxylic acid amides derived from 2- hydroxy-naphthalene-3-carb0xylic acid and the dithiazol from 4:4'-diaminodipheny1 or 4 4'-diamino-3:3'-dimethyldiphenyl are prepared in a similar manner.

Further amides of the same type are obtained by combination of the hydroxycarboxylic acids mentioned in the individual examples with the a'minothiazols' of other examples. In this Way, other amines, such as OH on .Q-Ne 5 6H N N in") CH: CH3

- .s 1 s o i "i t I) W 1 5111 N I N. o 6H.

etc., are obtained.

Example 7 "dll'uting the mixture with 300 parts of water dilute acetic acid is added until the reaction is feebly acetic. A diazosolution from 25.4 parts of 2' :4-dichloro-2'-aminodiphenylether which has been diazoti'zed. in knew-n.- manner, is allowed to fine suspension, while. stirring.

Ezvample 8 Cotton yarn is impregnated with an aoueous solution containing per liter-1.5 parts of the amide from 2-hydroxynaphthalene-3-carboxylic acid 15 and 2-amino-6-ethoxy-benzthiazol, 3 parts by volume of sodium hydroxide solution 0136" B.

and 5 parts by volume of Turkey red oil and 3 cc. of ethyl alcohol, thoroughly wrung out and sodium acetate which corresponds per liter to 2 parts of 2 amino 4:4 dichlorodiphenylether. intensive; pure 7 blue-red shade is obtained Twhieh has very good fastness properties.

5 Sueh arylides can be'used also for printing and for piece goods dyeing. 1 The procedure'is similar with the new amides and di'azocomponents obtained according to the dataofthe'present'introduction; If the new am- 1 ides do not possess such a pronounced aflinity for fthecellulosefib'er; as is the case with the amides from hydroxy carboxylic' acids of the benzene series, the use of more concentrated baths is recon'i- "men'ded'; I c

The following table contains a numberfof "shades obtainable from diazo components as'indicated in the present introduction and from amides obtainable from hydroxy-carboxylic acids and 2 -aminoarylthiazols or analogues thereof as developed in a diazo solution neutralized wit .20 indicated. in the introduction.

Goupllngeoinponeut: hydroxycarboxylle Shade of the dyeing D1820 companent acid amide fromon cotton 1 l-amino-Z'nltrobenzeue 1 mol: 2 -hydroxy-naphthalene-3-oarboxylic acid+ Brownish red.

. 1 iammo-B-ethoxy-benzthiazol. 2 l-amino-3-chlorobenzene do- Red. 3 l-amino-2:5-dichlorn n Brownish red. 4 l-amino-2-methoxy-fi-nitrobenzene Red. 5 4:4dichloro-2-amino-diphenylether Blulsh red. 6 l-amiuo-2-methoxy-dchlorobenzem Do. 7 V l-amino-2-methoxy-4 nitrobenzena Bordeaux. 8 l-amino-2-nitro-4-chlorobenzenel Red. .9 l-amino-2-methyl-i-chlorobenzeue Do. 10 Aminoazotoluene Reddisll violet. ll 1-amino-2-chlorobenzene B w 12 l-aminobenzeue -Z-carbox ic Do. 13 1-amino-2 methyl-3-chlorobenzene Red. 14 l-amino-2-methyl-3-nitrobenzene Do. 15 l-am1no-2-methyl-5-ohlorobenzen Bluish red. 16 l-amino-2-nitro-4-methyibenzene Red. 17 l-amino-2-methy1-4-mtrobenzene Bordeaux. 18 l-phenylazo-4-amino-5-methoxybe Violet. 19 l-amino-2-nitro+methoxyben1 m Bordeaux; 20 4-(4'-methy1)-pl1enoxy-acetylamino-2:5-dimethoxy-l-aminoben- Violet. zene. 21 4-1)enzoylamino-5-methyl-2-methoxy-l-amin" do 7 Reddish violet. 22 4-(2-methyl)-phenoxy-acetylamino-zdd ethoxy-l-aminobenzene. Navy blue. 23 4-( i'methyl) phenoxy-acetylamino-2:5-d1ethoxy-1-aminof do Reddishblue. 24 4-benzoylammo-ZziS-diethoxy-lwe --d Navy blue. 25 2':4-dichloro-2-amino-diphenyleiher Red. 26 4-ehloro-4-carbethoxy-2-aminodipheuylether Bluish red 27 4:4-d.iamino-3:3'-dimethoxy-2:2-dxchlordiphenyl do Do. 28 4'-methyl-4chloro2-amin0diphenylether Do. 29 2'-methyl-2-aminodiphenylether l 7 Red. 30 4'-methoxy-4chloro-2-amino-diphenylether do Bluish red. 31 4-amino-4'-methoxy-dipenyl min Navy blue. 32 2-methyl-4-ehloro-2-amino-diphenylether do Red. 33 l amino-bnitrobenzene 2 mp1s; Z-hydroxynephthalene-dearboxylie acid+ Brownish orange.

dithiazol from 4:4-d1aminodiphenylether. 34 l-amino-3-ohlorobenzene d Do. 35 l-amino-2-carboxylic acid-(4-chloro)-phenylester. do Do. 36 l-amino-Zzfi-dichlorobenzene Do. 37 l-amino-2-methoxy-d-nitrobenzene Red. 33 4-ehloro-2-amino-diphenylether- Do. 39 l-amino-2-methoxy-5-el1lorobenzene D0. 40 1-amino-2-methoxy-4-nitrobenzeua.- Bordeaux. 41 1-amino-2-nitro-4-methylbenzene Red. 42 1-amino2-methyl4-chlorobenzene Do. 43 Ortho-amidoazotoluene Reddish. violet. 44 l-amino-2'nitro-4-methoxybenzene Bordeaux. 45 4-(4'-methyl)-phenoxyacetylamino-2.E dimetl1oxy-l-ammoben- Reddish blue.

zene. I 46 4-benzoylaminoZ:E-diethoxy-l-aminobenzene do- Blue. 47 l-amino-Z-nitrohenzene l-hydroxy-4methylbenzene-2-cai-boxylic acid-+1 Violet brown. moi: 2-amino-6-ethoxybenzthiazol. 7 4s l-amino-El-ehlorob n efle do.;; Reddish brown. 49 1-amino-2z5-dichloroaniline .'.---do. Do. 50 2-amino-4:2'-dichlorodiphenyletherdo. Brown. 51 2-amino4:4'-dichlorodiphenylether- 1-hydt0xy-4methylbenzene-2-carboxylic acid+ Do.

1 molgieaminodethoxybenzthiazol. 52 2-amino-4-chlorodiphenylether do- Do. 4 53 l-amino-z-methoxy-fl-ehlorobenzen do Yelloyvish brown. 54 2-amine-4-chloro-4-carbethoxydiphenyleth do Reddish brown. 55 2-amino-l-methyl-5-nitrobenzene do Black brown. 56 2-methoxyphenylazo4'=amino-3'-m do Do. a 57 l-amino-2-nitro-4-methoxybenzene do Reddish brown. 58 l-amino-z'nitrobenzene 2m0ls 2-hy xyn xylic Red. 1 mo]: 2: 2'-diam1no-6: 6-diphenyldithiazol. 59 l-aminoe-ehlorobenzene --do Do. 60 l-amino-2: 5-dichloroanilinej D0- 1 zamino-iz 2-diohlorodiphenylether D0- 2 2-amino-4: 4'-dichlorodipheuylether-- D0- 63 2-amino-4-chlorodiphenylether D0- 64 l-amino-2-methoxy-S-chlorobenzene; B10181! red. 65 2-amino-4-ehloro--carbethoxydiphenylether Red. 66 7,amino-l-methyl-fi-nitrobenzene 31111 11 red. 67 2-methoxyphenylazo-4-amino-3-methylbenzene;- Bordeaux. 63 l-amino-znitro+methoxybenzene 7 Do. 69 4-benzoylamino-2: b-dlethoxyaminobenzen 7 Bluish hlack.

The dyestuffs of the numbers 2, 5, 10, 18,20, 24, 25, 28, 43, 50, 56, 61 and 69 of the foregoing table correspond to the following formulas:

No. 2 QN=III v s v I I OH: CHM OH:

OCH:

on. on l n I No.56 N=NGN=N-Q-E-NH-O s i H: No.61 Q-o-Qci on N ENH-G c-im-e -o'c'um N 09 O NH ll g A N cam on N N\ no r -m -o rcmz-c 5 v 3 8 S i WhatIclaim is: and naphthocarbauolenuclei, a: denote a whole 1. The caustic alkali-soluble amides of the for- I number not less than one and not greater than mm t two, and R1 stands for an aromatic radical to f which thesulfur atom and the nitrogen atom of o g the atom grouping (2-011 5- s- B J: 410N214: B; 7 --Q 1 N- N- H are united in orthc-positi onto one another.

wherein R stands for an aromatic radical se- The caustic alkalbscluble amides 1 t iected from the group consisting of a. benzene nu-. general fqrmula. cleus containing a methyl group in para-position 0H to the OH group, a. benzene nucleus containing a.

chlorine atom in para-position to the OH group, I3 fi f and naphthalene, carbazole, diphenyiene oxide H are united in the ortho-position to one another.

3. The amides of the general formula in which :2: denotes a whole number not less than one and not greater than two, and R1 stands for an aromatic radical to which the sulfur atom and the nitrogen atom of the atom grouping are united in the ortho-position to one another.

4. The amides of the general formula in which R1 stands for an aromatic radical to which the sulfur atom and the nitrogen atom of the atom grouping are united in the ortho-position to one another.

5. The amides of the general formula -ou1 s Ol?I-C m g H \N/ a in which R1 stands for an aromatic radical of the benzene series to which the sulfur atom and the nitrogen atom of the atom grouping are united in the ortho-position to oneanother.

6. The amides of the general formula in which the alkyl radical does not consist of more than 2 carbon atoms.

ERNST HENZI. 

